611-21-2

Usage

Uses

Used in Pharmaceutical Industry:
N-METHYL-O-TOLUIDINE is used as a reactant for palladium-catalyzed coupling reactions, which are crucial for the synthesis of various pharmaceutical compounds. These reactions allow for the formation of new chemical bonds and the creation of complex molecules that can exhibit therapeutic properties.
Used in Chemical Research:
In the field of chemical research, N-METHYL-O-TOLUIDINE is utilized as a reactant for palladium-catalyzed amination of bromoindazoles. This application is significant for the development of new chemical entities and the exploration of novel reaction pathways, contributing to the advancement of organic chemistry and its applications.
Overall, N-METHYL-O-TOLUIDINE plays a vital role in the synthesis of complex organic molecules and has potential applications in various industries, including pharmaceuticals and chemical research. Its use in palladium-catalyzed coupling and amination reactions highlights its importance in the development of new compounds and the advancement of chemical synthesis techniques.

Synthesis Reference(s)

Tetrahedron, 42, p. 4027, 1986 DOI: 10.1016/S0040-4020(01)87558-X

InChI:InChI=1/C8H11N/c1-7-5-3-4-6-8(7)9-2/h3-6,9H,1-2H3

Upstream product

• 917-64-6 methyl magnesium iodide 
• 60-29-7 diethyl ether 
• 88-72-2 1-methyl-2-nitrobenzene 
• 6380-09-2 toluene-4-sulfonic acid-(N-methyl-o-toluidide) 
• 5877-55-4 N-benzylidene-2-methylaniline 
• 77-78-1 dimethyl sulfate 
• 95-53-4 o-toluidine 
• 67-56-1 methanol 
• 14983-92-7 methyl N-(2-methylphenyl)carbamate 
• 67-66-3 chloroform 
• 609-72-3 N,N-dimethyl-o-toluidine 
• 80573-83-7 N-allyl-N-methyl-o-toluidine 
• 119515-89-8 N-Methyl-O-propyl-N-o-tolyl-hydroxylamine 
• 50-00-0 formaldehyd 

Downstream Products

• 573-26-2 N-methyl-N-(2-methylphenyl)acetamide 
• 28059-58-7 N-(2-methylphenyl)-N-methylbenzylamine 
• 66087-60-3 N-methyl-N-(o-methylphenyl)benzamide 
• 13508-78-6 N-methyl-2-methylchloroacetanilide 
• 100861-57-2 N,N-diethyl-glycine-(N-methyl-o-toluidide) 
• 609-72-3 N,N-dimethyl-o-toluidine 
• 52209-63-9 N-methyl-N-(2-methylphenyl)carbamoyl chloride 
• 6370-28-1 N,N'-dimethyl-4,4'-diamino-3,3'-dimethyldiphenylmethane 
• 408529-52-2 N,N'-dimethyl-N,N'-di-o-tolyl-methylenediamine 
• 80573-83-7 N-allyl-N-methyl-o-toluidine 
• 860677-97-0 2,2,2-trichloro-1-(3-methyl-4-methylamino-phenyl)-ethanol 
• 20632-28-4 N-Methyl-N-o-methyl-phenyl-harnstoff 
• 2058-63-1 2,N-dimethyl-4-o-tolylazo-aniline 

Relevant academic research and scientific papers

Synthesis of N-Alkyl Anilines from Arenes via Iron-Promoted Aromatic C-H Amination

We report both an intermolecular C-H amination of arenes to access N-methylanilines and an intramolecular variant for the synthesis of tetrahydroquinolines. A newly developed, highly electrophilic aminating reagent was key for the direct synthesis of unprotected N-methylanilines from simple arenes. The reactions display a broad functional group tolerance and employ catalytic amounts of a benign iron salt under mild reaction conditions.

CO2-tuned highly selective reduction of formamides to the corresponding methylamines

We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.

Method for realizing N-alkylation by using alcohols as carbon source under photocatalysis

The invention discloses a method for realizing N-alkylation by using alcohols as a carbon source under photocatalysis, and belongs to the technical field of catalytic synthesis. Alcohol, a substrate raw material and a catalyst are placed in a reaction device, ultraviolet and/or visible light irradiation is carried out in an inert atmosphere, after the irradiation is finished, solid-liquid separation is carried out to remove the catalyst, and an N-alkylation product can be obtained through extraction, distillation and purification, wherein the substrate raw material comprises any one of an amine compound, an aromatic nitro compound or an aromatic nitrile compound, the alcohol comprises any one or more of soluble primary alcohols, and the catalyst is metal oxide/titanium dioxide or metal sulfide/titanium dioxide. The method is simple and easy to operate, can be used for efficient photocatalysis one-pot multi-step hydrogenation N-alkylation reaction, and is mild in reaction condition, high in chemical selectivity of N-alkylamine, good in catalyst stability and easy to recycle.

Effect of the ancillary ligand in N-heterocyclic carbene iridium(III) catalyzed N-alkylation of amines with alcohols

A series of air-stable N-heterocyclic carbene (NHC) Ir(III) complexes (Ir1-6), bearing various combinations of chlorine, pyridine and NHC ligands, were assayed for the N-alkylation of amines with alcohols. It was found that Ir3, with two monodentate 1,3-bis-methyl-imidazolylidene (IMe) ligands, emerged as the most active complex. A large variety of amines and primary alcohols were efficiently converted into mono-N-alkylated amines in 53–96% yields. As a special highlight, for the challenging MeOH, selective N-monomethylation could be achieved using KOH as a base under an air atmosphere. Moreover, this catalytic system was successfully applied to the gram-scale synthesis of some valuable compounds.

Efficient methylation of anilines with methanol catalysed by cyclometalated ruthenium complexes

Cyclometalated ruthenium complexes4-10allow the effective methylation of anilines with methanol to selectively giveN-methylanilines. This hydrogen autotransfer procedure proceeds under mild conditions (60 °C) in a practical manner (NaOH as base). Mechanistic investigations suggest an active homogenous ruthenium complex and β-hydride elimination of methanol as the rate determining step.

Methoxycarbonylation of Alkyl-, Cycloalkyl-, and Arylamines with Dimethyl Carbonate in the Presence of Binder-Free Zeolite

Abstract: Methyl N-alkyl-, N-cycloalkyl-, and N-arylcarbamates were synthesized by reaction of the correspondingamines with dimethyl carbonate in the presence of binder-free FeHY zeolite. Theoptimal conditions (reactant ratio, amount of the catalyst, temperature,reaction time) were found to afford the target products with high yields.

P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C-N Coupling with Nitromethane as a Methylamine Surrogate

The direct reductive N-arylation of nitromethane by organophosphorus-catalyzed reductive C-N coupling with arylboronic acid derivatives is reported. This method operates by the action of a small ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide) together with a mild terminal reductant hydrosilane to drive the selective installation of the methylamino group to (hetero)aromatic boronic acids and esters. This method also provides for a unified synthetic approach to isotopically labeled N-methylanilines from various stable isotopologues of nitromethane (i.e., CD3NO2, CH315NO2, and 13CH3NO2), revealing this easy-to-handle compound as a versatile precursor for the direct installation of the methylamino group.

Selective N -monomethylation of primary anilines with the controllable installation of N -CH2D, N -CHD2, and N -CD3units

The selective N-monomethylation of primary anilines was realized by the use of the Me3N-BH3/N,N-dimethylformamide (DMF) system as the methyl source. This method also allows for the controllable introduction of N-CH2D, N-CHD2, and N-CD3 units with high lev

EffectiveN-methylation of nitroarenes with methanol catalyzed by a functionalized NHC-based iridium catalyst: a green approach toN-methyl amines

Compound [IrBr(CO)2(κC-tBuImCH2PyCH2OMe)] featuring a flexible pyridine/OMe functionalized NHC ligand κ1C coordinated efficiently catalyzes the selectiveN-monomethylation of nitroarenes using methanol as both the reducing agent and the C1 source. A range of functionalized nitroarenes including heterocyclic or sterically hindered derivatives have been efficiently converted to the correspondingN-monomethyl amines in good yields at low catalyst loadings using sub-stoichiometric amounts of Cs2CO3as a base. Mechanistic investigations support a borrowing-hydrogen mechanism in which methanol acts as the hydrogen source and methylating agent. Further, the hydrogen transfer reduction of nitrobenzene to aniline under optimized reaction conditions should proceed through a direct mechanism involving nitrosobenzene andN-phenylhydroxylamine intermediates.

Selective mono-N-methylation of nitroarenes with methanol catalyzed by atomically dispersed NHC-Ir solid assemblies

A series of N-heterocyclic carbene-iridium (NHC-Ir) coordination assemblies based on bis-pyrenoimidazolium salts are prepared, and shown to function as efficient solid molecular catalysts in selective mono-N-methylation of nitroarenes with methanol under mild conditions. The atomically dispersed active Ir(I) centers and the large π-conjugation rings endow the solid catalysts with an exceptionally high activity and selectivity for a broad substrate scope. Such solid NHC-Ir coordination assemblies are robust, which can be easily recovered and reused more than 10 runs without significant loss of their catalytic activity and selectivity. When combined with a subsequent formylation using the same solid catalysts under ambient conditions, this novel protocol can afford diverse formamides in excellent yields, further highlighting the applicability of the present solid catalysts for an efficient diversification of nitroarenes to a broad number of functional amines.